Flavoring with sulfur containing compounds

ABSTRACT

The flavor of a foodstuff is altered by use of an alkane dithiol, mercaptoalkanol, alkane dimercapto sulfide or alkane hydroxy mercapto sulfide of the formula WHEREIN X is oxygen or sulfur, n is 0 or 1, R-R9 are the same or different and each is hydrogen or lower alkyl of 1-4 carbon atoms, and at least one of R8 or R9 is such lower alkyl; a and b are the same or different and each represents an integer of from 0 to 10 when n is 0; and when n is 1, a and b are the same or different and each represents an integer of from 1 to 10.

United States Patent Wilson et al.

3,892,878 July 1, 1975 FLAVORING WITH SULFUR CONTAINING COMPOUNDS [75]Inventors: Richard A. Wilson, Westfield;

Christopher Giacino, Califon, both of NJ.

International Flavors & Fragrances Inc., New York, NY.

[22] Filed: Apr. 25, 1973 [21] App]. No.: 354,304

[73] Assignee:

[52] US. Cl. 426/534; 426/589; 426/203;

426/221; 426/222; 426/531; 260/609 R [51] Int. Cl A231 1/26 [58] Fieldof Search 426/65, 175, 221, 222,

[56] References Cited UNITED STATES PATENTS 3,043,880 7/1962 Fournier eta1. 260/609 R 3,394,016 7/1968 Bidmead et a1 426/250 3,653,920 4/1972Brinkman et a1. 426/65 3,713,848 1/1973 Katz et a1 426/65 3,773,52411/1973 Katz et a1 426/65 Primary ExaminerRaymond N. Jones AssistantExaminer-Esther L. Massung Attorney, Agent, or FirmBrooks l-laidtHaffner &

Delahunty [5 7] ABSTRACT The flavor of a foodstuff is altered by use ofan alkane dithiol, mercaptoalkanol, alkane dimercapto sulfide or alkanehydroxy mercapto sulfide of the formula (cR R s (CR4R R7 R8 c (SH)2 14Claims, No Drawings IFLAVUMING WITH SULFUR CONTAINING COMPOUNDSBACKGROUND OF THE INVENTION This invention has to do with altering theorganolep tic properties of foodstuffs. More particularly. the inventionrelates to the use of certain alkane dithiols mercapto alkanols, alkanedimercapto sulfides or alkane hydroxy mercapto sulfides to alter theflavor characteristics of a foodstuff. Contemplated are processes andcompositions for altering the flavor of foodstuffs.

The term alter in its various forms is used herein to mean the supplyingor imparting ofa flavor or aroma characteristic or note to an otherwisebland, relatively tasteless or non-odorous substance, or augmenting anexisting flavor or aroma characteristic where the natural flavor orintrinsic odor is deficient in some regard, or supplementing theexisting flavor or aroma impression to modify its quality, character,taste or aroma.

The term foodstuff as used herein includes both solid and liquidingestible materials which usually do, but need not have nutritionalvalue. Thus, foodstuffs include meats, gravies, soups, conveniencefoods, beverages, dairy products, candies, vegetables, cereals, softdrinks, snacks and the like.

The reproduction of roasted meat, vegetable flavors, poultry flavors andother roasted flavors has been the subject of a long and continuingsearch by those engaged in the production of foodstuffs. The shortage offoods, especially protein foods, in many parts of the world has givenrise to a need for utilizing non-meat sources of protein and for makingsuch protein as palatable and meat-or poultry-like as possible. Inaddition, various techniques utilized in processing food detract fromtheir flavor quality or give rise to off-flavors. Convenience or snackfoods are increasing in volume and they require flavoring. Accordingly,materials capable of closely simulating, improving, or even exactlyduplicating the flavor and aroma of roasted products and meat, poultryand vegetable products have long been sought.

PRIOR ART Various alkane thiols and alkane mercapto sulfides have beensuggested as flavoring agents. Thus, U.S. Letters Pat. No. 3,653,920which issued on Apr. 4, 1972 states that certain alkane thiol sulfides,such as 2-thiobutane thiol, can be used to impart a meat flavor tofoods; and United States application Ser. No. 135,377, filed Apr. I9,1971, describes various branched chain alkane thiols, such as 2-methyl3-butane thiol, and suggests their use for imparting roasted meat aromaand taste. None of these compounds are alkane dithiols or mercaptoalkanols, however.

SUMMARY OF THE INVENTION In accordance with this invention a newclass orclasses of sulfur-containing compounds, various alkane dithiols,mercapto alkanols, alkane dimercapto sulfides and alkane hydroxymercapto sulfides have been pro vided for altering the meat, poultry,vegetable or other roasted flavor of foodstuffs. Suitable sulfurcontaining compounds found useful in this regard may be represented by2'13 SH R (I: (CR2R3) a s (CR R .2 R7 R1 R6 *9 R8 C (SH) wherein X isoxygen or sulfur, n is O or 1, each of R, R,, R R R R R R R and R is thesame or different and each is hydrogen or lower alkyl of 1 through 4carbon atoms, and at least one of R and R is said alkyl; a and b are thesame or different and each represents an integer of from 0 through 10when n is O; and, when n is l, a and b are the same or different andeach represents an integer of from 1 to 10.

Among the alkane dithiols found especially useful are3,3-dimethyl2,2-butane dithiol and those of the formula SH SH 1o f 14 15a f 13 wherein a is 0 through 7, each of R through R is the same ordifferent and each is hydrogen or lower alkyl of from 1 to 3 carbonatoms. Included among such alkane mercapto thiols are:

l,2-ethane dithiol 1,2-propane dithiol 1,3-butane dithiol 2,3-butanedithiol l,3-propane dithiol 1,6-hexane dithiol l,4-butane dithiol1,4-pentane dithiol 1,2-butane dithiol 1,9-nonane dithiol 1,8-octanedithiol 1,5-pentane dithiol 2,4-pentane dithiol 3-methyl-l,5-pentanedithiol Z-methyl-l ,B-butane dithiol Among the alkane dimercaptosulfides and alkane hydroxy mercapto sulfides especially found suitableaccording to this invention are those represented by the formula XH 1920 f R16 i i S f 22 1 17 18 1 23 5 wherein X is sulfur or oxygen, andeach of R through R is the same or different and hydrogen or lower alkylof from l-3 carbon atoms, preferably methyl. Such al- 3 kane dimercaptosulfides and alkane hydroxy mercapto sulfides include:

I. di-a-methyl-B-mercapto propyl sulfide SH H CH CH 2.oz-methyl-B-mercapto-propyl-a-methyl-B- hydroxy propyl sulfide SH OH CHH-CH-S-CII-lH-CH H CH 3. Z-mercaptoethyl sulfide SH SH Among themercapto alkanols found especially suitable are those represented by theformula DESCRIPTION OF THE PREFERRED EMBODIMENTS The alkane dithiols,mercapto alkanols, alkane dimercapto sulfides and alkane hydroxymercapto sulfides of this invention are primarily useful in meat andpoultry flavor compositions although they may also be used in dairy andfruit flavors. They are especially suitable as flavors by reason of thewide range of useful concentrations at which they can be applied. Mostfla- 5 vor chemicals become objectionable in character at some point nottoo greatly above their threshold value. The alkane dithiols, mercaptoalkanols, alkane dimercapto sulfides and alkane hydroxy mercaptosulfides of the present invention have been found to be still suitableand inoffensive at proportions well in excess of their threshold valueand substantially above the multiple of their threshold at which otherflavor chemicals are objectionable.

The threshold value of the alkane dithiols, mercapto l5 alkanols, alkanedimercapto sulfides and alkane hydroxy mercapto sulfides may range from0.002 parts per million to 0.2 parts per million and, therefore,normally would be used at levels of from about 0.002 parts per millionto about 10 parts per million, but can actually be used withoutimparting an objectionable character up to about parts per million basedon the total weight of the foodstuff.

The actual amount used will vary depending upon a variety of factorsincluding the particular flavoring agent used, the flavor effectdesired, cost considerations, the amount and type of other ingredientspresent, the foodstuff to be flavored and the processing and storageconditions to which the foodstuff will be subjected. It should be keptin mind that larger concentrations do not necessarily give equivalentincremental flavor enhancement. In those instances where the alkanedithiols, mercapto alkanols, alkane dimercapto sulfides and alkanehydroxy mercapto sulfides are added to the foodstuff as an essential andintegral part of a flavoring composition, it is necessary that the totalquantity of flavoring composition employed be sufficient to yield aneffective alkane dithiol, mercapto alkanol, alkane dimercapto sulfideand alkane hydroxy mercapto sulfide concentration, i.e. sufficient toalter the organoleptic characteristics to which it is added orincorporated.

Suitable alkane dithiols, mercapto alkanols, alkane dimercapto sulfidesand alkane hydroxy mercapto sulfides according to this invention areshown in the following tabulation which includes a description of theflavor character of the compound at a typical use concentration noted inparts per million (ppm).

TABLE I USE COMPOUND FLAVOR CONCENTRA- TION CHARACTER (PPM) l,2-ethanedithiol roasted meat 0.5 l,2-propane dithiol bloody. tangy 0.5l.3-butane dithiol serumy 0.15 2,3-butane dithiol stewed beef 0.15Lil-propane dithiol skunky potent 0.05 1,6-hexane dithiol fatty,chicken. raw

' 'rty 0.05 l.4-butanedithiol metallic, garlic chemical 0.013.3-dimethyl-2,2-hutane dithiol eggy 0.25 LZ-butanc dithiol sweet. soft.grassy.

meaty 0.05 1,4-pentanc dithiol metallic, garlic,

chemical, harsh 0.05 l.9-nonane dithiol burnt meaty 0.5 v1,8-octancdithiol fatty. slightly roasted. chicken. dirty 0.051.5-pentanedithiol .sulfury, roasted meat 0.] Z-mercapto-S-butanolsweet. meat. stcwlike 0.5

TAB LE I Continued Di-a-methyl-B-mercapto propyl sulfideu-methyl-B-mercaptopropyl-a'-methyl-fi'- hydroxy propyl sulfideZ-mercaptoethyl sulfide 2,4-pentane dithiol light roasted meat metallic,liver-like meaty, roasted. onion The alkane dithiols, mercapto alkanols,alkane dimercapto sulfides and alkane hydroxy mercapto suI- fidescontemplated as flavoring agents by the present invention are oldcompounds and may be prepared by conventional or analogous techniques.For example, 2,3-butane dithiol is prepared by reacting 2,3-epoxy butanewith ammonium thiocyanate at room temperature and atmospheric pressureto obtain 2,3- epithiobutane which, in turn, is treated with sodiumhydrosulflde in a solvent (e.g. ethanol) and the 2,3- butane dithiolobtained is recovered. Di-a-methyLB-mereapto-propyl sulfide anda-methyl- B-mercapto propyl-a-methyl-B-hydroxy propyl sulfide as well as2-mercapto-3-butanol are also obtained in this reaction, though in minorproportion to 2,3- butanedithiol. The alkane dithiol,l,4-pentane-dithiol, is prepared by reacting l,4-dibromopentane withthiourea at elevated temperature and then treating the reaction productwith an alkalimetal hydroxide such as potassium hydroxide to obtain thedesired product. The alkane dithiol 3,3-dimethyl-2,2-butane dithiol isprepared by reacting 3,3-dimethyl-butane-2-one with hydrogen sulfide atlow temperature (-5 to +5C) in the presence of dry hydrogen chloride,and the desired product is recovered.

The alkane dithiols, mercapto alkanols, alkane dimercapto sulfides andalkane hydroxy mercapto sulfldes described herein may be employed eithersingly or in admixtures comprising two or more thereof. Admixtures oftwo or more alkane dithiols, mercapto alkanols, alkane dimercaptosulfides and alkane hydroxy mercapto sulfides offer the advantages ofcombining the beneficial and organoleptic qualities of each of thecompounds into a total impact which is superior or different from thecharacteristias of the sole ingredient. The formulator can simulate awide variety of organoleptic characteristics to evoke a predeterminedtaste response on the part of the consumer.

Generally in use the alkane dithiols, mercapto alkanols, alkanedimercapto sulfides and alkane hydroxy mercapto sulfides are admixedwith one or more auxiliary flavoring adjuvants. The precise adjuvantsemployed will depend upon the ultimate use contemplated and theorganoleptic character desired. Flavoring adjuvants are recognized inthe art and are ingestibly acceptable or non-toxic. Such flavoringadjuvants include stabilizers, thickeners, surface active agents,conditioners, flavorants and flavor intensifiers.

Stabilizers include preservatives, e.g., sodium chloride, antioxidants,e.g., calcium and sodium ascorbate, ascorbic acid, butylatedhydroxyanisole (mixture of 2 and 3 tertiary butyl-4-hydroxyanisole),butylated hydroxy toluene (2,6-di-tertiary-butyl-4-methyl phenol),propyl gallate and the like, sequestrants, e.g., citric acid.

Thickeners include carriers, binders, protective colloids, suspendingagents, emulsifiers and the like, e.g., agar-agar; carrageenan;cellulose and cellulose derivatives such as carboxymethyl cellulose andmethyl cellulose; natural and synthetic gums such as gum arabic, gumtragacanth; and proteinaceous materials such as gelatin; lipids,carbohydrates; starches; pectins and emulsifiers, e.g., monoanddiglycerides of fatty acids.

Surface active agents include emulsifying agents, e.g. fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, monoand diglycerides of fatty acids, lecithin, defoaming andflavor-dispersin g agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like; buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcunin and thelike; firming agents such as alluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers; anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferric pyrophosphate, ferrousgluconate and the like; riboflavin vitamins; zinc sources such as zincchloride, zinc sulfate and the like.

Flavorants and flavor intensifiers include organic acids, e.g., fattysaturated, unsaturated and amino acids; alcohols, e.g., primary andsecondary alcohols; esters; carbonyl compounds including aldehydes andketones; lactones; cyclic organic materials including benzenederivatives; alicyclics, heterocyclics such as furans, pyridines,pyrazines and the like; sulfurcontaining materials including thiazoles,thiols, sulfldes, disulfides and the like; so-called flavor potentiatorssuch as monosodium glutamate, guanylates, inosinates; natural andsynthetic flavorants such as vanillin, natural gums and the like;spices; herbs; essential oils and extractives including anise, aniseoil, alkanet root extract, bay leaves, capsicum extract and the like.

The specific flavoring adjuvant selected for use may be either solid orliquid, depending upon the desired physical form of the ultimateproduct, i.e., foodstuff, whether simulated or natural, and should, inany event, be capable of providing an environment in which the alkanedithiols, mercapto alkanols, alkane dimercapto sulfides and alkanehydroxy mercapto sulfides can be dispersed or admixed to provide ahomogeneous medium. In addition, selection of one or more flavoring 7adjuvants as well as the quantities thereof will depend upon the preciseorganoleptic character desired in the finished product; thus, in thecase of flavoring compositions, ingredient selection will vary inaccordance with the foodstuff to which the flavor and aroma are to beimparted. In contra-distinction, in the preparation of solid products,e.g., simulated foodstuffs, ingredients capable of providing normallysolid compositions should be selected such as various cellulosederivatives.

The preferred flavoring adjuvants which are used in combination with atleast one alkane dithiol, mercapto alkanol, alkane dimercapto sulfideandalkane hydroxy mercapto sulfide include: 4-methyl-5-(B-hydroxyethyl)thiazole, ethyl thioacetate, furfural, benzaldehyde, methional,hexanal, diacetyl, amyl alcohol, ethyl disulfide, methyl mercaptan,2,4-decadienal, 2,4- decadienol,2,5-dimethyl-2,5-dihydroxy-1,4-dithiane, 1,3-dithiolane, Z-mcthyll,3-dithiolane, 3,5-dimethyl- 1,2-dithiolane, 3-methyl-1,2-dithiolane,2,4-dimethyl- 1,3-dithiolane, 4-methyl-1 ,3-dithiolane, 1,2-dithiane,1,3-dithiane, 1,4-dithiane, 2-methyl-l,3-dithiane, 2,4-dimethyl-1,3-dithiane, 4-methyl-l,3-dithiane, 2,4,6-trimethyl-1,3-dithiane, thiamine hydrochloride, 2-methyl- 1-butanethiol, 3-mercapto-2-pentanone, furfuryl alcohol, 2-mercaptopropionic acid, methyl pyrazine, 2-ethyl-3-methyl pyrazine,tetrahydrofurfuryl alcohol, tetrahydrothiophen- 3-one, tetramethylpyrazine, dipropyl disulfide, methyl benzyl disulfide, 2-buty1thiophene, 2,3-dimethy1 thiophene, S-methyl furfural,3-acety1-2,5-dimethy1furan, guaiacol, phenyl acetaldehyde,'y-decalactone, dlimonene, acetoin, amyl acetate, maltol, ethylbutyrate, levulinic acid, piperna1, ethyl acetate, n-octanal, npentanal,2-isobuty1 thiazole, propyl propenyl disulfide, propyl propenyltrisulfide, 2,6-dimethyl pyrazine, acetophenone, 2-methyl-2-butena1,furfuryl mercaptan, acetyl propionyl.

Flavoring compositions prepared in accordance with the present inventionpreferably contain alkane dithiol, mercapto alkanol, alkane dimercaptosulfide and alkane hydroxy mercapto sulfide in concentrations rangingfrom about 2 X 10' to 25% by weight, based on the total weight of saidflavoring compositions, but may contain as much as 80 or 90% by weightof the alkane dithiol, mercapto alkanol, alkane dimercapto sulfide andalkane hydroxy mercapto sulfide compound, if the flavoring compositionis then applied in small amount.

All parts, proportions, percentages arid ratios herein are by weightunless otherwise indicated.

It will be understood by those skilled in the art that the alkanedithiol, mercapto alkanol, alkane dimercapto sulfide and alkane hydroxymercapto sulfide can I be added to the materials to be flavored oraromatized at any convenient point in the production of the consumablematerial by any of the conventional techniques including spray drying,blending, stirring, dissolving and the like. Thus, when they are used toalter or otherwise vary the flavor of a foodstuff, theycan be added inthe original mixture, emulsion, preparation, or the like, prior to anycooking or heating operation. A1- ternatively, they can be added at alater stage of processing if volatilization losses wouldbe excessiveduring the earlier processing.

The following examples are given to illustrate embodiments of theinvention as it is now preferred to practice it. It will be understoodthat these examples are illustrative, and the invention is not to beconsidered as restricted thereto except as indicated in the appendedclaims. I Y Y 4-mercapto2-butanone,'

EXAMPLE 1 The following materials are homogeneously admixed at 25C:

Ingredients Parts Furfural 1.0 Benzaldehyde 0.5 Mcthional 1.0

10 n-Hexanal 3.0 2,4-Decadiena1 5.0 L-hexanedithiol 25.0 Ethanol (95%aqueous) 63.5

The resulting mixture has an excellent chicken aroma with pleasant fattynuances.

EXAMPLE II The composition prepared in Example 1 is dissolved inpropylene glycol to provide an 0.1% solution. This solution in theamount of 0.966g is added to 7.3g of a soup base consisting of:

Ingredients Parts Fine ground sodium chloride 35.62 Hydrolyzed vegetableprotein 27.40 Monosodium glutamate 17.81 Sucrose 10.96 Chicken fat 5.46Caramel color 2.73

The resulting mixture is added to 12 025. of boiling water to obtain asoup having an excellent chicken flavor.

EXAMPLE III The following are homogeneously admixed at 77F:

cooling to 100F, 0.12 part of diacetyl and 0.10 part of hexanal areadded. The resulting mixture has an excellent roasted sulfury meat note.

EXAMPLE Iv The following materials are homogeneously mixed at 77F:

Ingredients Parts -Continued Ingredients Parts Taurine 20.0 Mixture ofdi-sodium inosinate and di-sodium guanylatc 3.3

The mixture is heated at 300F for 30 Seconds. After cooling to 100F,0.12 parts of diacetyl and 0.10 part of hexanal are added. After agingthe resulting mixture' for three hours 0.1 ppm of l,5-pentanedithiol isadded. The resulting mixture is aged for hours to provide a materialhaving a sulfury, roasted meat aroma.

The mixture is heated at 300F for 30 seconds. After cooling to'lO0F,0.12 part of diacetyl and 0.10 part of hexanal are added. After agingthe resulting mixture for three hours 0.5 ppm of 2-mercapto-3-butanol isadded.

The resulting mixture is aged for 10 hours to provide a material havingan excellent sweet meaty note.

EXAMPLE VI Ingredients Parts Vegetable shortening Salt Glutamic acidL-Cysteine hydrochloride B-Alanine Taurine Mixture of di-sodiuminosinate and di-soclium guanylate Di-a-methylB-mercapto propyl sulfidea-Methyl-B-mercapto-propyl-a'- methyl-fl'-hydroxy-propyl sulfide I ppmThe resulting mixture has an excellent roasted meat aroma.

EXAMPLE VII The following ingredients are homogeneously mixed at 77C:

Ingredients Parts Vegetable shortening 622.7 Salt 321.7 Glutamic acid5.1 L-Cysteine hydrochloride 10.3 Glycine 5.1 B-Alanine 1.3 Taurine 20.0Mixture of di-sodium inosinate and di-sodium guanylate 3. 3

The mixture is heated to 300F for30 seconds. After cooling to 100F, 0.12part of diacetyl, 0.10 part of hexanal, 0.5 ppm of I,2-ethanedithiol areadded. The

resulting mixture has an excellent roasted meat aroma.

EXAMPLE VIII The following ingredients are homogeneously mixed at 77C: I

Ingredients Parts Vegetable shortening 622.7

Salt 321.7 Glutamic acid 5. I

L-Cysteine hydrochlorid l0.3

Glycine 5.l

B-Alanine l.3

Taurine 20.0

Mixture of di-sodium .inosinate I and di-sodium guanylate 2.0

EXAMPLE IX a. Cysteine hydrochloride in the amount of 8.8g is refluxedat 215F under atmospheric pressure for four hours with a mixture of 309gof hydrolyzed vegetable protein, 8.8g thiamine HCI, and 674g of water.Subsequent to the reflux, the mixture is cooled and 0.15 ppm of2,3-butanedithiol is added and intimately admixed with the composition.The mixture has an excellent stewed beef flavor.

b. The beef favor produced in Example IX(a) is added to:

1. a commercial dry type pet food;

2. a semi-moist type pet food; and

3. wet or canned pet food.

When so added at levels of 0.5, 1, (by weight of foodstuff) highlypalatable pet foods are obtained.

EXAMPLE X The composition prepared in Example III is dissolved inpropylene glycol to provide a 0.1% solution. This solution in the amountof 0.966g is added to 7.3g of a soup base consisting of:

1.5. 2; 2.5 and 3% The composition of Example IV (0.005g) when added tothe above soup base also provides a soup having good meat flavor.

EXAMPLE XI The composition prepared in Example VIII is dis- 5 solved inpropylene glycol to provide an 0.1% solution.

This solution in the amount of 0.966g is added to 7.3g of a soupbase'consisting of:

Ingredients Parts Ingredients Parts Fine ground sodium chloride 35.62 F640 Hydrolyzed vegetable protein 5 Sodium chloride 320 (Maggi 4.35)27.40 Glutamic acid 5 Monosodlum glutamate l7-8l L-cysteinehydrochloride l Sucrose l0.96 B-alanine 2 Chicken fat 2.48 Glycerin:Caramel color Thiamine hydrochloride I0 Mixture of disodium inosinate l0and disodium guanylate 4 The resulting mixture is added to 12 ounces ofboiling water to obtain a soup having an excellent chicken fl Theforegoing mixture is continuously fed to a The composition of Example V(0.005g) when add d scraped wall heat exchanger where it is heated foroneto the above soup base also provides a soup having 15 half minute at325F. The mixture is then immediately good meat flavor. cooled at 100Fin a second scraped wall heat exchanger. EXAMPLE After cooling, 0.12parts of diacetyl and 0.10 parts of a. Preparation of Spray-DriedProduct hexanal are added. The mixture has a chicken flavor. Thefollowing ingredients are refluxed for 4 hours, preparation of ChickenFlavored Gravy aged for 3 days and spray-dried to produce a Solidproduct having a beef flavor. Before drying sufficient A "f for thepreRaranon of f f f gum arabic is added to provide a compositioncontaingravy prepared by blendmg the followmg mgredlems: ing 0.5 partsgum arabic and one part flavor solid.

Ingredients Parts I d' t. Parts ngrc len S Cornstarch 29 L-Cysteinehydrochloride 1.32 30 HOP 21 Carbohydrate-free vegetable chfckcn fat 1 1protein hydrolyzate 22.05 CH5) brand of y Ethyl thioacetate 22.00gcngted vegetable ml 11 Thiamine hydrochloride 1.32 Sodium chloride 9a-alanine 0.50 Monosodlum glutamate 5 Water 53.31 Chicken flavorprepared in Part (a) of this Example 7 Sucrose 2 Onion powder 0.50 T 'c0.05 b. Preparation of Beef Gravy zigf i Om 7 A beef gravy concentrateis produced by formulating wh'te pepper a gravy flavor composition ofthe ingredients and in the 40 i i amounts nd Gated To this mixture lSadded 0.5 ppm of l,8-

octanedithiol, 0.01 ppm of 1,4-butanedithiol and 0.l5 Ingredients Partsppm of l,3-butanedithiol. The mixture of the above Fl 34 30 threedithiols imparts to this gravy mixture an intense gg :5 =excellentchicken meat flavor character. Beef fat 61.20 About 10 parts of thegravy mixture is thoroughly dis- Sodium chloride 9.90 1 d 10 f l d ThMonosodium giutamate 720 perse in parts 0 coo e water. e lspersion ISCarbohydrate-free vegetable then brought to a boil and simmered for 2minutes. A ggg'fg'gigfigif figg .5 gravy having an excellent chickenmeat flavor is ob- White pepper 0.36 tained. The spray-dried product ofpart XII (a) above 5.40 EXAMPLE XIV a. Preparation of Flavor Mixture Tothis mixture lS added at the rate of 0.5 ppm, 1,2- The following mixtureis prepared: propanedithiol. The said dithlol improves the bloody, tangybeef extract flavor character of the mixture.

To one unit of said gravy flavor concentrate 24 ozs. Ingredients Partsof water are added, and the mixture is stirred thoroughly to dispersethe ingredients, brought to a boil, f zg ga m 53 0 simmered for 1 minuteand served. The meatless gravy S-Methyl furfural 5.0 obtained showsexcellent bloody, tangy beef extract fla- PP UflIflCO r. Methylmercaptan ,5 Tetrahydrothiophen-3-one 5.0 EXAMPLE XIII Methional L0Tetrahydrofurl'uryl alcohol 30.0

a. Preparation of Chicken Flavor The following mixture is prepared:

b. Preparation of Soup -Continued A beef noodle soup is prepared bymixing together: lngmdicms Pans Tetrahydroi'urfuryl alcohol 46.0Z-MethyI-Z-butenal 2.0 Furfuryl mercaptan 0.2 Onion oil 0.] IngredientsParts Acetyl propionyl 2.7

Sodium chloride 50 Mixture of Part (a) of g g f b. Preparation of BeefGravy gggfgfgggf 1 A beef gravy concentrate is made by formulating aGarlic powder 1 gravy flavor composition of the ingredients and in theWhite pepper. ground 6 Mixed vegetable base 360 amounts lndlcated'Ingredients Parts Three cups of water are added to the above mixture andthis mixture is brought to a full boil, simmered for lo r 34.20 fiveminutes and is then read to serve Cornstarch 3600 i y Beef fat 6l.20 The2,3-butaned1th1ol imparts a beef stew note to the Sodium chloride 9.90Monosodium glutamate 7.20 soup with a desirable brothy flavor.carbohydrateiree vegetable protein hydrolyzate 19.80 EXAMPLE XV Toastedonion powder 2.52 White pepper 0.36 a. Preparation of Flavor Mixture Themixture of PM (a) of s The following mixture is prepared: ExampleIngredients Pam To one unit of gravy flavor concentrate 24 ozs. of waterare added and the mixture is stirred thoroughly M SEY -B- y y y 5; 0 todisperse the ingredients. brought to a boil, simmered lflZ l 3pmpanedimiol Q05 ppm for 1 minute and served. This meatless gravy has anex- Amylalwhol 2-8 cellent roasted meat character primarily caused bythe m ga? gj presence of the Z-mercaptoethyl sulfide included in theDiacetyl 10.0 flavor mixture of Part (a) of this Example. Ethyldisulfide 3.0

EXAMPLE XVII 21. Preparation of Spray-Dried Product Preparation of ShakeComposmon The following ingredients are refluxed for 4 hours, A shake"composition for enhancing the flavor of aged for 3 days and spray-driedto produce a solid meats is prepared by admixing the followingingrediproduct having a beef flavor. Before drying sufficient ems: gumarabic is added to provide a composition containing 0.5 parts gum arabicand one part flavor solid.

Ingredients Parts Tumenc 251) Ingredients Parts Paprika 25.0 Oregano IL-cysteine hydrochloride L32 Monosqdlum glutamate 75 o Carbohydrate-freevegetable grmd) protein hydrolyzate 22.05 Sodium chloride (fine gr nd)550.0 Ethyl thioacemte 2100 Mlxwrc of (3) of 400 0 Thiaminehydrochloride L32 Example fi-alanine 0.50 Water 53.3l

When sprinkled on meat the above mixture imparts i and meat note effectand this effect ihereto an on (my y b. Preparation of Beef Gravy iscaused by the presence of 1,3-propaned1th1ol.

XVI A beef gravy concentrate is produced by formulating EXAMPLE a gravyflavor composition of the ingredients and in the a. Preparation ofFlavor Mixture amounts indicated.

The following mixture is prepared:

Ingredients Parts Ingredients Parts Flour 34.204-Methyl-5-B-hydroxyethyl Cornstarch 36,00 thiazole Beef fat 61.20Z-mercaptoethyl sulfide 0.5 ppm Sodium chloride 990 3 i rh pyrazine 4.0Monosodium glutamate 7,20 Acetophenone 3.0 Carbohydrate-free vegetablefi i l 1.0 protein hydrolyzate 19.80

-Continued Ingredients i Parts Toasted Onion powder 7 2.52 White pepper0.36 The spray-dried product of Part XVII('a) above 5.40

To this mixture is added, at the rate of 0.5 ppm, [,2- ethanedithiol.The said ethanedithiol improves the roasted meat flavor character ofthemixture.

To one unit of said gravy flavor concentrate 24 02s. of water are added,and the mixture is stirred thoroughly to disperse the ingredients,brought to a boil, simmered for 1 minute and served. The meatless gravyobtained shows excellent roasted meat flavor.

EXAMPLE XVIII a. Preparation of Chicken Flavor The following mixture isprepared:

Ingredients Parts Fat 640 Sodium chloride 320 Glutamic acid 5 YL-cysteine hydrochloride l B-alanine 2 Glycerine Thiamine hydrochlorideI0 Mixture of disodium inosinatc and disodium guanylatc 4 The foregoingmixture is continuously fed to a scraped wall heat exchanger where it isheated for onehalf minute at 325F. The mixture is then immediatelycooled at l0OF. in a second scraped wall heat exchanger.

After cooling. 0.12 parts of diacetyl and 0.10 parts of hexanal areadded. The mixture has a chicken flavor.

b. Preparation of Chicken Flavored Gravy A mixture for the preparationof chicken flavored gravy is prepared by blending the followingingredients:

White pepper To this mixture is added 0.25 ppm of 3,3-dimethyl-2,2-butanedithiol, 0.5 ppm of 1,2-butanedithiol and 0.5 ppm ofl,9-nonanedithiol. The mixture of the above three dithiols imparts tothis gravy mixture an'intense chicken meat flavor character. I I

EXAMPLE XIX a.,Preparation of Flavor Mixture The following mixture isprepared:

Ingredients Parts 4-Methyl -5fi hydroxyethyl thiazole 5 S-Methylfurfural Di-a-methyl-B-mercapto propyl sulfide Guaiacol Methyl mercaptanTetrahydrothiophen-3'one Methional Tetrahydrofurfuryl alcohol 3 b.Preparation of Soup A beef noodle soup is prepared by mixing together:

Ingredients Parts Maltol dextrin 25 Sodium chloride Mixture of Part (a)of this Example 5 Gelatin .IO Monosodium glutamate 4 Caramel color 4Garlic powder 1 White pepper. ground 6 Powdered mixed vegetable base 360Three cups of water are added to the above mixture and the mixture isbrought to a full boil. simmered for 5 minutes and is then ready toserve.

The Di-wmethyl-B-mercapto-propyl sulfide imparts a meaty body to thesoup with a desirable roasted chicken flavor.

EXAMPLE XX a. Preparation of Flavor Mixture The following mixture isprepared:

Ingredients Parts 4-Methyl-5-B-hydroxyethyl thiazole Amyl alcoholMethional Hexanal Diacetyl Ethyl disulfidea-Methyl-B-mercapto-propyloz'-methyl-B'-hydroxy propyl sulfide 1.0 ppmb. Preparation of Shake Composition A Shake composition for enhancingthe flavor of meats is prepared by admixing the following ingredients:

Ingredients Parts Tumeric 25.0 Paprika 25 .0 Oregano l 5.0 Monosodiumglutamate (fine grind) 25.0

-Continued ingredients Parts Sodium chloride (fine grind) 550.0 Mixtureof Part (a) of this Example 5.0 Maltol dextrin 3950 When sprinkled onmeat the above mixture imparts thereto a roasted meat note effect andthis effect is caused by the presence ofa-methyl-fimercaptopropyl-oz'-methyl-;8'-hydroxypropyl sulfide.

EXAMPLE XXI a. Preparation of Flavor Mixture The following mixture isprepared:

Ingredients Parts 4-Methyl-S-B-hydroxyethyl thiazole l.9-nonanedithiol2,6-Dimethyl pyrazine Acetophenone Guaiacol Tetrahydrofurfuryl alcoholZ-Methyl-Z-butenal Furfuryl mercaptan I Onion oil Acetyl propionyl b.Preparation of Beef Gravy A beef gravy concentrate is made byformulating a gravy flavor composition of the ingredients and in theamounts indicated.

Parts Ingredients Flour 34.20 Cornstarch 36.00 Beef fat 61.20 Sodiumchloride 9.90 Monosodium glutamate 7.20 Carbohydrate-free vegetableprotein hydrolyzate 19.80 Toasted onion powder 2.52 White pepper 0.36The mixture of Part (a) of this Example 5.40

To one unit of gravy flavor concentrate 24 ozs. of water are added andthe mixture is stirred thoroughly to disperse the ingredients, broughtto a boil, simmered for one minute and served. This meatless gravy hasan excellent burnt meaty character primarily caused by the presence ofthe 1,9-nonanedithiol included in the flavor mixture of Part (a) of thisExample.

EXAMPLE XXII Preparation of 2-Methyl-l,3-Butane Dithiol 18 cmpcolurnnipacked with 5 X 5 Ras'chig rings. A vacuum of 3 m nil-lg waspulled and fraction one was collected boiling between 25 and C. The rawdistillation was stopped at this point. The fraction collected wasdiscarded since it consisted of unreacted isoprene and raw thiolaceticacid. Approximately grams of the residue was mixed with approximately 50ml of Primol high viscosity mineral oil and transferred to a bantamwaredistillation apparatus. Under a vacuum of 1 mmHg, three fractions werecollected boiling between lO2 and 107C. The residue was discarded. Thethree fractions totalled approximately 85 g. The three fractions werecombined and mixed with 45 g of potassium hydroxide, 250 ml. of waterand 400 ml of ethanol and refluxed for 1 hour. The reaction'mix wascooledto room temperature and the ethanol stripped off on the rotaryevaporator. The aqueousresidu'e was neutralized with HCI (conc.) andextracted 2 times with ether, which was dried over Na SO (anhyd) andconcentrated on the rotary evaporator. Preparatory gas liquidchromatography on 8 feet X inch glass 5% Carbowax 20M 7, EXAMPLE XXlIlPreparation of B-Methyll ,S-Pentanedithiol In a 250 ml, 3-neckedround-bottomed flask equipped with an immersion thermometer, amechanical stirring apparatus, a water-cooled reflux condenser and a 250ml addition funnel was mixed 30 ml H 0 and 46 grams of thiourea. Themixture washeated to reflux and 50 grams of 3-methyl-l,S-dibrdmopentanewas added during 1 hour. The reflux was continued overnight and the nextmorning the viscous reaction mix was cooled to room temperature and 56grams of KOH in 100 ml H O was added. The reaction mix was refluxedunder a N atmosphere for 5 hours then cooled to room temperature. Agrayish precipitate hadformed in a yellowish liquid. The precipitate wasfiltered off and discarded. The filtrate consisted of two layers whichwere separated in a separatory funnel. The oil layer was dried overanhydrous Na SO and the aqueous layer was acidified (pH6) withconcentrated HCl during which more of the grayish precipitate wasformed. The mixture was extracted oncewith ether. The extract was driedand concentrated. There was negligible residue which was thereforediscarded. The 3-methyl-l,S-pentanedithiol was separated from the driedoil layer by preparative gas liquid chromatography on an 8 feet X inchglass 5% Carbowax 20M (polyethylene glycol-terephthalic acid terminated)column and its structure was confirmed by mass spectral analysis and NMRspectroscopy.

EXAMPLE XXIV Preparation of 2,3-Butanedithiol anda-Methyl-B-Mercapto-Propyl-a'-Methyl-B-l-lydroxy Propyl Sulfide, anddi-a-MethyLB-Mercapto-Propyl Sulfide and 2-Mercapto-3-Butanol ln a literErlenmayer flask was dissolved at room temperature 184 gms. of ammoniumthiocyanate in 400 ml. of H 0, 152 grams of 2,3-epoxy butane was added by slowly pouring it in. The flask was stoppered, gently slurried andplaced in the hood where it remained for 3 days. A light brown oil phaseseparated out which was removed in a separatory funnel. This was slowlypoured into a solution of 250 grams of NaSH X H O in 1500 ml of 95%ethanol. The reaction mixture was allowed to stand overnight. It wasnext divided into three equal parts. Each was mixed with four volumes ofwater and extracted once with 200 ml of ether. The combined ethers wereback-extracted once in IN KOl-l. The aqueous phases were acidified (pHwith concentrated HCl and extracted twice with ether. The alkaline etherextract was dried and concentrated to a yellow oil. The acid ether wasdried and concentrated to a light yellow oil. Gas liquid chromatographyon the acid ether extract showed several large peaks. Each was trappedfor analysis. Trap No. 2 was 2,3- butanedithiol. Trap No. l was2-mercapto-3-butanol. Trap No. 3 was a-methyl-B-mercapto-propyl-a'-methyl-B-hydroxy propyl sulfide. Trap No. 4 was di-a-methyl-B-mercaptopropyl sulfide. Trap No. 5 was identical to the major component from thealkaline ether extract and was identified as 3,4,6,7-tetramethyl-1,2,5-trithiepane. The structures of the compounds were confirmed bymass spectral analysis and NMR spectroscopy.

What is claimed is:

l. A process for altering the organoleptic properties of a foodstuffwhich comprises adding thereto an effective amount of asulfur-containing compound of the formula wherein X is oxygen or sulfur,each of R through R is the same or different and each is hydrogen orlower alkyl of l-4 carbon atoms, and at least one of R or R is suchlower alkyl; and when n is 0, then b is O and a is an integer of from 0to 7; and when n is l, a and b are the same and each represents aninteger of l.

2. The process of claim 1 wherein said compound is of the formula sliaSH 1o C 14 a- 13 wherein a is 0 through 7, each of R through R is thesame or different and each is hydrogen or lower alkyl of from 1 to 3carbon atoms.

3. The process of claim 2 wherein said compound is l,2-ethanedithiol.

4. The process of claim 2 wherein said compound is 2,3-butanedithiol.

20 5. The process of claim 2 wherein said compound is 1,6-hexanedithiol.

6. The process of claim 1 wherein said compound is represented by theformula xn R19 R20 SH l l l l wherein each of R through R is the same ordifferent and each is hydrogen or lower alkyl of from 1 through 3 carbonatoms.

11. The process of claim 10 wherein said compound is2-mercapto-3-butanol.

12. The process of claim 1 wherein said compound is3,3-dimethyl-2,2-butane dithiol.

13. A flavor altering composition comprising at least onesulfur-containing compound of the formula T 19 20 R16 1i 5 C 22 17 18 212 wherein X is sulfur or oxygen, and each of R through R is the same ordifferent and each is hydrogen or lower alkyl of from 1 through 3 carbonatoms, and an auxiliary flavoring adjuvant selected from the groupconsisting of stabilizers, flavorants, and flavor intensifiers.

14. A flavor altering composition comprising at least onesulfur-containing compound of the formula as on wherein each of Rthrough R is the same or different and each is hydrogen or lower alkylof from 1 through 3 carbon atoms, and an auxiliary flavoring adjuvantselected from the group consisting of stabilizers, flavorants, andflavor intensifiers.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,892,878 DATED July 1, 1975 |NVENTOR(S) I RICHARD A. WILSON andCHRISTOPHER GIACINO it is certified that error appears in theab0ve-identified patent and that said Letters Patent are herebycorrected as shown below:

Col. 11, Example XII, in the tabulation under "Ingredients" "oi-alanine"should read Balanine--.

Signed and Scaled this sixth D y of January 1976 [SEAL] A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ufPurentsand Trademarks

1. A PROCESS FOR ALTERING THE ORGANOLEPTIC PROPERTIES OF A FOODSTUFFWHICH COMPRISES ADDING THERETO AN EFFECTIVE AMOUNT OF ASULFUR-CONTAINING COMPOUND OF THE FORMULA
 2. The process of claim 1wherein said compound is of the formula
 3. The process of claim 2wherein said compound is 1,2-ethanedithiol.
 4. The process of claim 2wherein said compound is 2,3-butanedithiol.
 5. The process of claim 2wherein said compound is 1,6-hexanedithiol.
 6. The process of claim 1wherein said compound is represented by the formula
 7. The process ofclaim 6 wherein said compound is di- Alpha -methyl- Beta -mercaptopropyl sulfide.
 8. The process of claim 6 wherein said compound is Alpha-methyl- Beta -mercapto-propyl- Alpha ''-methyl- Beta ''-hydroxy propylsulfide.
 9. The process of claim 6 wherein said compound is2-mercaptoethyl sulfide.
 10. The process of claim 1 wherein saidcompound is represented by the formula
 11. The process of claim 10wherein said compound is 2-mercapto-3-butanol.
 12. The process of claim1 wherein said compound is 3,3-dimethyl-2,2-butane dithiol.
 13. A flavoraltering composition comprising at least one sulfur-containing compoundof the formula
 14. A flavor altering composition comprising at least onesulfur-containing compound of the formula